聚紫精-脂肪酸盐表面活性剂复合物的组装合成及相行为研究

通过Menshutkin反应合成聚(对亚二甲苯基-4,4'-联吡啶二溴)(PXV)半刚性链聚紫精,采用等量混合法将聚紫精与系列不同碳链长度的阴离子表面活性剂脂肪酸钠Cn-1COONa(n=10,12,14,16,18)组装制备聚电解质-表面活性剂(PXV-Cn)复合物,运用DSC,TGA,XRD,FTIR等表征手段初步考察复合物的超分子结构及相行为.基于FTIR谱学分析特征、小角与广角变温XRD数据以及DSC热分析焓变的定量计算结果,表明半刚性主链聚紫精和脂肪酸盐极性头基组成的极性层与侧链烷烃非极性层交替排列形成层状超分子结构,其中烷烃链靠近极性端约8个亚甲基处于无定型态,其余碳链则形成结晶相.最短的PXV-C10形成少量规整度较低的三斜晶βT,n≥16以上的长碳链复合物则以六方相αH为主,其它中等长度侧链脂肪酸盐复合物则为多种结晶形式共存.随着碳链长度n的增加,侧链结晶熔点Tm升高,n≥16的长碳链复合物表现出随温度变化的可逆结晶相态变化.且这类聚紫精-表面活性剂复合物表现出高于200℃的热稳定性.     

Organocatalytic asymmetric synthesis of α-amino esters from sulfoxonium ylides

Described here is the first organocatalytic asymmetric N–H insertion reaction of α-carbonyl sulfoxonium ylides. Without a metal catalyst, this reaction represents an attractive complement to the well-established carbene insertion reactions. As a stable surrogate of diazocarbonyl compounds, sulfoxonium ylides reacted with a range of aryl amines to provide efficient access to α-aryl glycines with excellent enantiocontrol in the presence of a suitable chiral phosphoric acid catalyst. The high stability and weak basicity of sulfoxonium ylides not only enable this protocol to be user-friendly and practically useful, but also preclude catalyst decomposition, which is crucial to the excellent amenability to electron-poor amine nucleophiles. Detailed mechanistic studies indicated that the initial protonation is reversible and the C–N bond formation is rate-determining.

An organocatalytic asymmetric N–H insertion reaction of α-carbonyl sulfoxonium ylides has been developed to provide efficient access to α-amino esters without involving a metal carbenoid intermediate.     

Visible‐Light‐Driven Overall Water Splitting Boosted by Tetrahedrally Coordinated Blende Cobalt(II) Oxide Atomic Layers

Directly splitting water into H₂ and O₂ with solar light is extremely important; however, the overall efficiency of water splitting still remains extremely low. Two types of ultrathin semiconductor layers with the same elements and the same thicknesses were designed to uncover how different atomic arrangements influence water‐splitting efficiency thermodynamically and kinetically. As an example, tetrahedrally coordinated blende and octahedrally coordinated rocksalt CoO atomic layers with nearly the same thicknesses were synthesized for the first time. The blende CoO atomic layers have a smaller E_g and abundant d–d internal transition features relative to the rocksalt CoO atomic layers, which ensure enhanced visible‐light harvesting ability. Density functional theory calculations reveal that the Bader charge for Co atoms in blende CoO atomic layers is larger than that of the rocksalt CoO atomic layers, which facilitates photocarrier transfer kinetics, as verified by photoluminescence spectra and time‐resolved fluorescence emission decay spectra. In situ FTIR spectra and energy calculations reveal that the *OOH dissociation step is the rate‐limiting step, where the blende CoO atomic layers possess a smaller *OOH dissociation energy thanks to their higher Bader charge and stronger steric effect, as confirmed by the elongated Co?OOH bonds. The blende CoO atomic layers exhibit visible‐light‐driven H₂ and O₂ formation rates of 4.43 and 2.63 μmol g^?1 h^?1, roughly 3.7 times higher than those of the rocksalt CoO atomic layers.     

In Situ Engineering of Intracellular Hemoglobin for Implantable High‐Performance Biofuel Cells

The key challenge for the broad application of implantable biofuel cells (BFCs) is to achieve inorganic–organic composite biocompatibility while improving the activity and selectivity of the catalysts. We have fabricated nanoengineered red blood cells (NERBCs) by an environmentally friendly method by using red blood cells as the raw material and hemoglobin (Hb) embedded with ultrasmall hydroxyapatite (HAP, Ca₁₀(PO₄)₆(OH)₂) as the functional BFC cathode material. The NERBCs showed greatly enhanced cell performance with high electrocatalytic activity, stability, and selectivity. The NERBCs maintained the original biological properties of the natural cell, while enhancing the catalytic oxygen reduction reaction (ORR) through the interaction between ?OH groups in HAP and the Hb in RBCs. They also enabled direct electron transportation, eliminating the need for an electron‐transfer mediator, and showed catalytic inactivity for glucose oxidation, thus potentially enabling the development of separator‐free BFCs.     

Boron Nitride Membranes with a Distinct Nanoconfinement Effect for Efficient Ethylene/Ethane Separation

A BN membrane with a distinct nanoconfinement effect toward efficient ethylene/ethane separation is presented. The horizontal and inclined self‐assembly of 2D BN nanosheets endow the BN membrane with abundant percolating nanochannels, and these nanochannels are further decorated by reactive ionic liquids (RILs) to tailor their sizes as well as to achieve nanoconfinement effect. The noncovalent interactions between RIL and BN nanosheets favor the ordered alignment of the cations and anions of RIL within BN nanochannels, which contributes to a fast and selective ethylene transport. The resultant membranes exhibit an unprecedented separation performance with superhigh C₂H₄ permeance of 138 GPU and C₂H₄/C₂H₆ selectivity of 128 as well as remarkably improved long‐term stability for 180 h, outperforming reported state‐of‐the‐art membranes.     

A fluorescent sensor based on quinazoline ketone derivatives for selectivity of Fe3+

In this work, we provided a fluorescent sensor based on a compound containing fluorophore quinazoline ketone for detecting metal ions. 2-Methyl-4(3 H)-quinazoline thione was synthesised as a fluorescent probe for tervalent ferric ion (Fe³⁺) detection. Fluorescent determination of 2-methyl-4(3 H)-quinazoline thione indicated its maximum emission wavelength of 306.5 nm. The fluorescence interference and titration experiments have shown that the compound has a high selective fluorescence response to Fe³⁺. With an increase in the Fe³⁺ ion concentration, the fluorescence emission strength gradually weakened, and a slight red shift appeared. With Job’s method, 2-methyl-4(3 H)-quinazoline thione was proved to form a 1:2 complex with Fe³⁺. The results revealed that 2-methyl-4(3 H)-quinazoline thione could be used as a fluorescent probe for the recognition of Fe³⁺ with high selectivity.     

Optical readout method for microcantilever array sensing and its sensitivity analysis

An optical readout platform using a knife-edge filter for detecting the bending of a bimaterial microcantilever array is established, and the influence of stress-induced micromirror deformation on the optical detection sensitivity is discussed. The influence of deformation is modeled theoretically and validated experimentally. Analysis shows that the optical detection sensitivity will decrease by 50% when the mirror has a deformation of lambda/5 (lambda is the wavelength of readout light). Finally, an infrared image is obtained by the platform.     

基于N次图像旋转法的两平晶三面互检技术研究

光学平面面形的绝对检验技术规避了干涉仪参考面形精度的制约,能够有效提高平晶面形的检测精度。采用N次图像旋转法的两平晶三面互检的绝对检验技术,求解待测平晶的三维绝对面形分布,结果中包含了中频波段的信息。利用递推公式构造旋转变化项的N次虚拟旋转结果,求和平均后得到旋转变化项,叠加旋转不变项结果后得到待测波面面形。推导了算法的理论误差,针对旋转角度进行优化并增加虚拟旋转次数,提高了算法精度,优化后的仿真结果的残差波面的均方根值精度为0.14 nm。对150 mm口径平晶进行两平晶三面互检实验,并将实验结果与传统三面互检法结果进行比对,均方根值偏差小于0.5 nm,验证了算法的准确性。     

丙酮酸分子结构与振动光谱的密度泛函理论研究

用密度泛函方法BLYP、B3LYP和从头算Hartree-Fock(HF)方法在6-31G*基组水平上对丙酮酸分子的几何结构（甲基的重叠式和交错式两种构象）和振动光谱分别进行了优化和计算,并给出了各种频率所对应的红外强度及拉曼活性,对光谱进行了指认。结果表明：在丙酮酸分子的两种构象中,重叠式比较稳定*B3LYP计算得到的构型参数与实验结果比较一致;在振动频率的计算中,BLYP未标度力场所计算的非CH3伸缩振动基频预测值和实验值的平均绝对偏差为10.4cm-1;而HF标度力场的平均绝对偏差为17.9cm-1。说明两者的结果与实验观测频率比较吻合,但B3LYP的频率计算值偏差（38.3cm-1）较大。根据振动频率的势能分布和红外光谱强度对此分子的振动基频进行了理论归属。     

十二醇聚乙二醇醚分子量分布与其溶液界面性能的关系

利用高纯单一十二醇聚乙二醇醚C₁₂E_n摸似配制Gauss分布型混合物,测定其水溶液的表面张力、增溶量及去污率。实验结果表明,聚乙二醇链长不同分布的醇醚混合物属于理想混合。混合溶液的Γ_∞、Πcmc 随分布宽度增加而增大。形成表面吸附膜及胶束时,短 EO 链分子占先。胶束溶液对乙苯的增溶量随分子中EO数增多而增大。宽分布C₁₂E_n的去污率优于窄分布,但在一定分布范围内,其影响不显著。